Vitreous decalcomania



Patented Feb. 24, 1953 VITREOUS DECALCOMANIA Harry 0. Rathke, Chicago,111., assignor to The Meyercord Company, Chicago, 111., a corporation ofIllinois Application July 23, 1948, Serial No. 40,316

1 Claim. 1

This invention relates to decalcomanias and more particularly to avitreous type of decalcomania and a method of preparing and applying thesame to chinaware, pottery or the like.

Heretofore, one of the principal disadvantages in producing surfacedecorations on chinaware, pottery or the like by means of designs whichare transferred from decalcomania paper to a surface to be decorated andthen fired, was the tendency of the vitreous material forming the designto improperly fuse to the article surface and to form minute pits,bubbles, blisters or voids during the firing operation. These designimperfections resulted primarily from the action of the gases of thesolvents, binder and other consumable material in the body of thetransfer as they escaped or attempted to escape therefrom as the firingtemperatures were increased.

In some instances the design layer or layers were formed on top of asupporting film which was relatively impervious like the design layerand which wa placed against the surface to be decorated so as tounderlie the design layer during firing. The disadvantage of thisconstruction was that the gases which formed upon decomposition of thesupporting film forced their Way up through the design layer and causedimperfections therein. Moreover, because the design layer was separatedby the supporting film from the article surface, the design layer didnot fuse down properly into the surface of the article when fired. Theformation of gases and the consequent boiling action of the under layertended to hold the design material away from the article surface.

Such types of decalcomanias were also applied to the surface of anarticle by means of a special china cement or adhesive which wasmanually applied to the article surface by a brush after which thetransfer portion of the decalcomania was applied thereagainst and rubbeddown. However, it was quite difficult, if not impossible, to apply thespecial adhesive in a thin, smooth film due to the brush method ofapplication and also to the fact that evaporation of solvents andchanges of room temperature during use caused the consistency of theadhesive to thicken and the ingredients thereof to separate in thecontainer. Furthermore, from day to day, the

brushes and the adhesive were not properly sealed or protected from theair so that oxidation of the adhesive caused the formation of minuteparticles'or solids. If the adhesive was applied in a thick, uneven coator had oxidized particles therein, the finished fired product would bewholly unacceptable since the gases of these concentrations of adhesivewould form eruptions and pits in the design surface.

Moreover, it has been found that even if the special adhesive, whichusually comprised some sort of varnish containing a resin, was appliedin a thin, smooth film nevertheless gases were formed and a boilingaction took place under the design layer or under the supporting filmand, in order to escape, the gases necessarily forced their way upthrough the design layer spoiling the appearance of the finished design.

Another disadvantage of the use of adhesive was the impossibility ofcorrectly positioning the transfer once it had been applied thereto.Because the adhesive was sticky, the transfer could not be slid aboutinto the desired position so that if proper positioning was not achievedon first contact, the transfer would have to be removed and rewashedalong with the article surface. This constituted a loss of labor as wellas materials thereby increasing the ultimate cost of the finishedarticle. Then, after the transfer had been correctly positioned, it wasnecessary to rub it down with soap and a brush to clean the transfer andarticle surface and to secure an intimate contact. This operation wasagain entirely manual and was particularly a laborious job where largeproduction was being attempted. Quite often as the transfer was beingcleaned and pressed down under considerable pressure into the adhesive,minute wrinkles and air pockets were formed in the transfer and betweenthe transfer and the adhesive without the operator being aware of theirformation and, consequently, the design was improperly fused to thearticle, and bore surface imperfections.

After the transfer was so positioned over the adhesive, the decalcomaniapaper was then removed by the application of Water to dissolve the watersoluble adhesive.

minute particles were fused into the surface which should have remainedclear, causing noticeable specks or discolorations and rendering thefinished article commercially unacceptable.

A further inherent disadvantage of the adhesive method of applicationresulted from the necessity of permitting the adhesive to dry beforefiring. This not only was time consuming but required a manufacturer tomaintain a large area for storage purposes.

For many years workers in the ceramic and decalcomania ants have beenattempting by various proposed means and methods to overcome theabove-mentioned difficulties and disadvantages, but for one reason oranother and in spite of the claims made in the patented art coveringsuch means and methods, they have proven relatively unsatisfactory andcommercially unacceptable. The trade, therefore, for lack of anysatisfactory solutions, has thus continued to tolerate the old methodsand the old type of decalcomanias above described and has assumed asinevitable the burden of a great percentage of spoilage and loss runningas high as twentyfive per cent in many instances.

It is, therefore, one of the objects of the present invention to providean improved form of vitreous decalcomania for application to chinaware,pottery or the like and an improved method of forming and applying thesame.

Another object of the invention is to provide a ceramic decalcomaniawhich may be merely slid off the paper backing and applied to a surfaceto be decorated without the use of a special sticky adhesive and withoutrequiring a waiting period to permit drying of the special adhesive,thus eliminating factory storage space, permitting proper positioningand immediate firing and eliminating the damage caused by the escape ofthe adhesive gases during firing,

Still another object is to provide a ceramic decalcomania comprising adesign layer, composite or single in form, supported on a flexible filmand comprising vitrifiable material, the design layer being formeddirectly on the soluble adhesive coating of the decalcomania paper andadapted to be released therefrom and applied directly against thesurface to be decorated, the remaining thin film of water solubleadhesive serving to adhere the transfer to the article surface.

A further object is to provide a ceramic decalcomania having a designlayer and a supporting layer or film on the top surface thereof, the toplayer or film being comprised of two incompatible or immisciblematerials which penetrate down into the design layer upon applicationthereto, thereby forming a design and outer supporting film which isheterogeneous in nature and minutely granular or open, thus permittingthe gases generated during firing in the design and supportin film toreadily escape without causing surface imperfections.

A further object of the invention is to provide a method of applying adesign to a ceramic article which comprises forming a design layerdirectly on the soluble adhesive coating of decalcomania paper, forminga flexible supporting film over said design layer, separating the designlayer and supporting film from the paper backing by dissolving theadhesive coating, applying the design layer directly against the ceramicarticle with the supporting film on the outer surface thereof, theremaining soluble adhesive serving to adhere the transfer to the articlesurface, and then firing the same.

Another further object is to provide a method of applying ceramicdecalcomania of the simplex or duplex type which comprises aligning amultiplicity of finished decalcomanias in stacks and securing the sametogether, immersing the entire stack in water and removing the same,sliding the transfer from the paper backin as they are required forapplication to chinaware or the like, applying the same to the chinawarewithout the use of a special adhesive, and then immediately firing thesame.

Another object is to provide a decalcomania of the foregoing characterin which the supporting film is on the top surface of the design layerso that upon firing the gases of the tough supporting film need not passup through the design layer to disturb the same.

Other and further objects and advantages of the invention will becomeapparent hereinafter from the description which follows and by referenceto the accompanying drawing in which:

Figure 1 is a diagrammatic, vertical sectional view of a ceramicdecalcomania of the simplex type comprising a preferred embodiment ofthe present invention;

Fig. 2 is a diagrammatic, vertical sectional view of the transferportion of the decalcomania prior to firing after it has been slid offthe aper backing and applied to the surface of an article of chinawareto be decorated;

Fig. 3 is a diagrammatic, vertical sectional view showing the designlayer of the decalcomania after it has been fired and fused into thupper surface of the article of chinaware;

Fig. 4 is a diagrammatic, vertical sectional view of a duplex type ofdecalcomania embodying the present invention; and

Fig. 5 is a diagrammatic, vertical sectional view of the manner in whicha plurality of decalcomanias may be arranged in stacks for rapidhandling and application.

The decalcomania illustrated in Fig. 1 of the drawing and comprising apreferred embodiment of the present invention is of the simplex type. Itcomprises an absorbent paper backing l0 having a coating ll ofchemically pure hydrolized starch which is water soluble and permits thetransfer portion, presently to be described, to be separated from thepaper backing [0. The design layer [2 is illustrated diagrammatically inthe drawing as a single layer applied onto the releasable coating II butit is to be understood that it more frequently may be arranged as acomposite layer with overlapping strata and areas and perhaps with abackground film, .and may comprise a plurality of colors formed adjacentto each other in the desired outline and design. The design layer forthe purposes of the present invention comprises the design that isfinally fused onto the article to be decorated.

The design film l2 may be applied to the soluble adhesive coating II byvarious methods, such as screen printing, lithography, rotogravure andthe like, although for beauty of design and proper shading and diversityof colors, the lithograph method has been found quite satisfactory. Thematerial of which the design film I2 is composed is a pure resinousvarnish and a quantity of pulverized glass of the desired color, andthis film may be applied by either of two methods. By one method, thepulverized glass may first be thoroughly mixed in with the varnish priorto a vitreous ink to the releasable coating II.

printing and then the mixture may be appliedas 01'. if desired, thevarnish may be printed directly onto the coating I I and then thepulverized glass may be dusted on in theusual manner while the varnishis still wet. Whichever method is employed, the design layer is formedonly after a plurality of printing's in order to secure the variouscolors and shadings of colorsin the design, each printing being allowedto dry before the next successive printing is applied.

After the design layer I2 has been completed and is dried, then a cleartransparent, flexible supporting film or carrier layer I3, whichcomprises one of the novel features of the present invention, is appliedover the top thereof. This supporting carrier film I3 is comprised of atleast two incompatible or immiscible substances and a solvent. Forexample, the material of the film may comprise 124 ounces of ethylcellulose mixed into paste form with a quantity of anhydrous alcohol. Tothis paste, is added approximately 4 ounces of polymerizedmethyl-methacrylate resin and then the entire mixture is dissolved in 'aquantity of solvent comprising butyl alcohol. The quantity of solventthat is added may vary in accordance with the proper consistencyrequired by the method of printing employed.

The ethyl cellulose and the polymerized methyl-methacrylate resin areincompatible or immiscible with each other, and even after thoroughagitation of the mixture, the resultant mass is still heterogeneousrather than homogeneous. The minute droplets of polymerizedmethyl-methacrylate are separately interspersed between separate minutedroplets of ethyl cellulose. The structure of the mass is, therefore,composed substantially of disunited globular units or particles withoutany bonding medium to hold such units or particles together, and afterthe fiowable mixture has been applied as a covering supporting film I3and has dried, the disunitel, heterogeneous character as above describedis still present. The dried film is, thus, more or less granular or openand still in the form of minute separate units or particles as comparedto an impervious surface.

The same characteristic is also imparted to the design layer I2 by thesupporting film I3. Although the design layer I2 as applied to thereleasable coating I I and dried, is relatively homogeneous andimpervious, nevertheless, when the mixture comprising the supportingfilm I3 is applied in a wet state thereover, the design layer I2 issoftened by the solvent in the later applied film. As a consequence, theethyl cellulose and the polymerized methyl-methacrylate resin penetratedown and merge to a certain degree into the resinous varnish and thepulverized colored glass so that the incompatible units or particles ofethyl cellulose and polmerized methyl-methacrylate resin each includeparticles of pulverized glass. Thus, the relatively impervious surfaceof the design layer I2 is opened up in a manner similar to thatdescribed with respect to the carrier film I3.

The important result of the relatively open or non-impervious nature ofthe carrier film l3 and the design film I2 is that when the design andcarrier layers have been transferred to the chinaware and are beingfired at relatively high temperatures, the gases generated by theburning and decomposition of the binder materials and solvents of eachlayer may readily escape up between and from the minute particles intothe atmosphere. Because the openings are minute and extend over theentire area, no large concentrations of gases are formed in pockets norare the gases forced to push their way up through a relativelyimpervious surface under great pres-- sure so as to cause blistering,bubbling or pitting of the surface; The gases merely take the easiestavenues of escape which are already provided between the minutedivisions or particles.

Whefithe article is fired with the transfer appliedthereon, the clearsupporting film I3 is burned away as well as the varnish binder in thedesign layer I2, leaving only the pulverized glass particles which underthe high temperature become fused into the outer surface of the articleas an integralpart thereof. The surface of the design is flat and smoothas shown in Fig. 3, and contains no imperfections therein rendering thefinal product unacceptable.

The method of application of the transfer to the article is extremelysimple but effective and involves none of the disadvantages or poorresults' of prior methods. No special adhesive or cement is required.The decalcomania illustrated in Fig. l of the drawings may be dipped inwater for a short period to partially dissolve the hydrolized starchlayer II and to permit the design layer I2 and its carrier film 3 to beslid therefrom. After being separated from the paper backing I!) thetransfer is then applied to the surface of the article to be decorated,the design coating I2 being placed directly against the article surfaceas shown in Fig. 2. Although most of the hydrolyzedstarch is dissolvedby the water, a sufilcient quantity remains in the under surface of thedesign layer I2 and serves to adhere the composite transfer film to thearticle. However, the hydrolyzed starch is not of the extremely stickynature as the resinous varnishes which have been heretofore employed asthe special cement, and consequently the composite transfer film may bereadily slid about on the article surface into the desired positionprior to firing.

During application of the composite film to the article, the topsupporting film I3, which is flexible and tough, serves as a carrier andholds the various projecting parts of the design in their properrelative positions. Positioning of the design is facilitated by thetransparency of the supporting film. Also because of the intimate bondwhich has been established between the carrier film I3 and the designlayer I2, no particles of the design are permitted to break away whenthe transfer is released from the paper backing I0 so that whentransferred the design remains intact.

When the composite transfer has been properly positioned on the articlesurface, it is then rubbed down lightly and gently with a soft rubbersqueegee in order to eliminate any air pockets and effect intimatecontact with the article surface, care being taken, however, not todisturb the position thereof on the surface. The rubbing pressure thatis applied is very slight since it is unnecessary to force the transferdown into intimate contact with any special adhesive or to smooth outany irregularities in the adhesive. Since the hydrolized starch itselfserves as the adhesive and is carried by the transfer, it is disposed ina thinner, smoother and more regular film than any special adhesivecould ever be applied by a brush or any other method.

7 Another-and greatly important advantage resulting from the eliminationof the use of a special and separately applied adhesive as a means ofcausing the transfer to adhere to the chinaware prior to and duringfiring, is the fact that the relatively great volume of gases which weregenerated therefrom and therein during firing have been eliminated.Heretofore, when special resinous adhesives were employed, a boilingaction occurred and the gases which were generated by the heat collectedin concentrat ed areas and forced their way up through the design layerto the atmosphere, thus causing imperfections therein. However, thehydrolized starch in comparison to such resinous adhesives is not causedto boil or become highly active under heat, but on the contrary quietlydecomposes without affecting the design layer in any way.

Furthermore, because the design layer I2 is substantially in directcontact with the surface of the article and is not separated therefromby a relatively thick layer of special adhesive, or a supporting film,the contact of the fusible material in the design layer with the articlesurface is more intimate and the layer 12 is not caused to be forcedaway therefrom by the boiling action of any special adhesivetherebeneath. When the temperatures are sufiiciently high to liquefy theouter skin of the article of chinaware, the liquified vitrifiablematerial of the design layer is directly thereagainst and consequentlythe two substances readily merge as an integral surface without anyimperfections therein, as shown in Fig. 3.

The firing of the transfer into perfect fusion with the surface of thearticle of ware is also facilitated by preconditioning the transfer.This preconditioning comprises the application of a mixture containing aplasticizer and a solvent for the design and carrier layers, to theouter surface of the carrier layer l3 which has the effect of causingthe layer 13 and the design layer l2 to become quite soft and toapproach their wet or semi-fluid condition as when first applied to thedecalcomania paper. By softening these layers, they are further openedup so that when the article is placed in a furnace immediately after thesolution has been applied to the transfer, the gases may escape morereadily than if the transfer had been placed in the furnace in a harddry state. As a result of this preconditioning, the firing period may bereduced to a much shorter time and production may therefore beincreased. Y

Because of the simplicity of structure of the decalcomania and themethod of applying the same without the use of any special adhesive,mass production methods of application to articles of ware by relativelyunskilled operators is made possible, and the results as evidenced bythe finished products are substantially perfect, the percentage ofspoilage being reduced to a very low minimum. A rapid method ofapplication of the transfer to an article also comprises an importantfeature of the present invention as it has enabled the production rateof decorative chinaware to be at least trebled. This rapid method, asshown in Fig. 5, comprises simultaneously cutting the decalcomanias 20from stacks of large sheets and arranging the cut stacks ofdecalcomanias in groups of one hundred, for example, each group beingheld together by adhe sive 2| on one side thereof similar to a pad ofpaper. When the operator then desires to apply a design onto an articleof chinaware, the entire pack is merely immersed in water for a suitableperiod of time to dissolve the soluble adhesive coating ll; then, afterremoval from the water. the pack may be placed by the operator on astand or table adjacent a supply of chinaware to be decorated, andfollowing which the design and carrier films may be progressivelyremoved one by one when application is desired. When the top transferportion has been removed and applied, its paper backing is turned ortorn off the stack thereby exposing the next transfer below, as shown inFig. 5.

In Fig. 4 of the drawing, the invention is shown as embodied in adecalcomania of the duplex type. This embodiment comprises a heavy paperbacking I5, a layer of adhesive l6 adapted to permit the backing [5 tobe separated from the rest of the transfer, a layer of thin tissue paperIT, a layer ll of water soluble adhesive such as hydrolized starch, thedesign layer I2 and the top supporting film I3. This duplex decalcomaniais prepared in a manner similar to that utilized in producing thesimplex type of Fig. l of the drawing and the application of thetransfer to the article of ware is also similar. These duplexdecalcomanias may be handled in the usual manner by stripping the thintissue paper I! from the paper backing I5 or they also may be arrangedin unified stacks of one hundred. If the latter method is followed, thewater in which they are immersed may be treated with a wetting agent soas to cause the tissue paper I! to remain firmly adhered to the paperbacking 15, thus permitting the films l2 and I3 to be readily removedfrom the tissue paper l'l, this removal action being similar to thesimplex type.

It is thus apparent that the novel form of ceramic decalcomania and themethod of producing and preparing the same for firing on chinaware andthe like have overcome all the difiiculties and disadvantages of theprior art decalcomanias and methods. No elaborate preparations orequipment are required and the necessity for skilled help has beeneliminated. The manufacturer of chinaware is assured of perfect firingand the great percentage of spoilage and loss has been eliminated, thusreducing the overall cost of production of the finished article.

Although there has been described above and illustrated in the drawingan improved form of ceramic decalcomania and a method of preparing andapplying the same, it is to be understood that modifications in thedetails of structure and composition of materials and in the steps ofthe methods may be resorted to without departing from the spirit andscope of the appended claim.

I claim:

A decalcomania comprising a water permeable backing coated with asoluble adhesive layer, a vitreous design layer on said adhesive layercontaining a pulverized vitrifiable material in a combustible binder,and a flexible supporting film disposed directly over design layer, saiddesign layer and said supporting film being releasable as a unit fromsaid backing to permit said design layer to be adhered to an article tobe decorated with said supporting film outermost, said supporting filmcomprising interspersed discrete particles of ethyl cellulose and apolymerized methyl methacrylate resin with said ethyl cellulose beingpresent in said film in a major proportion, and said supporting filmbeing partially merged with said design layer at the interfacetherebetween.

HARRY C. RA'I'HKE.

(References on following page) 9 10 REFERENCES CITED Number Name DateThe following references are of record in the 2,261,260 KFaus 1941 fileof this t 2,267,787 (312N012. D60. 30, 1941 2,271,192 Hinz Jan. 27, 1942UNITED STATES PATENTS 5 2,294,211 Rothrock Aug. 25, 1942 Number NameDate 2,359,185 Wysong Sept. 26, 1944 439,536 Maxwell Oct. 28, 18902,359,462 Bricker Oct. 3, 1944 493,449 Schmalz Mar. 14, 1893 2,385,920Jenkins Oct. 2, 1945 829,131 Wachter Aug. 21, 1906 2,445,084 Rehberg eta1. July 13, 1948 1,271,006 Becker July 2, 1918 0 2,475,802 OssermanJuly 12, 1949 1,996,549 McNutt Apr. 2, 1935 2,088,031 Miller July 27,1937 OTHER REFERENCES 2,154,193 Carr et aL 11, 1939 Hercules, EthylCellulose for Varmshes, 1939', 2,220,525 Kauppi et aL Nov. 5 1940 pages12, 14, inslde page of back cover.

2,235,514 Brown Mar. 18, 1941 15

